Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
  • C03C25/10—Coating
  • C03C25/24—Coatings containing organic materials
  • C03C25/26—Macromolecular compounds or prepolymers

Definitions

• This invention relates to the field of sizing compositions for glass fibers, and more particularly, for glass fiber gun roving, and to glass fibers coated therewith.
• Fibers used as reinforcing elements in polymeric or resinous matrix materials are usually coated witn a very light-weight size coating which serves to protect the fibers from damage by abrasion during processing, handling and/or use, to bind the individual fibers into more-or-less tightly integrated multi-fiber bundles or strands, and/or to ennance the reinforcing interaction between the fibers and the resinous matrix in which they are imbedded as reinforcing elements.
• Such sizing compositions are frequently applied to the glass fibers at the time of their initial production, which is ordinarily by pulling a plurality of streams of molten glass issuing from a reservoir thereof through a substantially corresponding plurality of suitable orifices so as to attenuate these streams to the desired fiber diameter as they cool and solidify.
• the sizing composition is typically applied to the individual fibers in-line as soon as they nave cooled sufficiently below the solidification temperature, which cooling may be accelerated by wetting the newly solidified but still hot fibers with water.
• Liquid sizing compositions are applied in such situations by spraying, by drawing the fibers across a suitable roll, belt, apron, pad, etc.
• liquid sizing composition wet with the liquid sizing composition, or other conventional liquid coating methods, after the liquid sizing composition has been applied to the individual advancing glass fibers, they are typically brought together while still at least partially wet with the liquid sizing composition into one or more multifiber bundles or strands, which may be collected into a suitable package for further processing, storage and/or shipment, as by winding onto a rotating collet.
• the wet fibers or strands are normally dried, before and/or after such collection, to deposit the non-volatile residue of the liquid sizing composition onto the surfaces of the fibers.
• Liquid sizing compositions suitable for such application to glass fibers ordinarily are dilute solutions, dispersions and/or emulsions, often in aqueous media, of a film-forming polymer or resin, a lubricant and a coupling agent.
• Other components such as anti-static agents (especially wnere the sized glass fibers are to be chopped into snort lengths while dry), emulsifying or sol ubili zing agents, viscosity modifying agents, etc. have also sometimes been incorporated in such liquid sizing compositions.
• gun roving which desirably consists of a plurality of continuous strands weakly integrated together, with each strand consisting of a plurality of individual glass fibers tightly integrated together by the size coating on the fibers.
• gun roving is used by feeding it through a suitable chopper incorporated in or closely associated with a suitable gun for spraying a fluid resin composition together with the chopped roving onto a mold or other suitable target so that the chopped roving or pieces of strand separated therefrom becomes imbedded in the fluid resin, which will subsequently be solidified by cooling ano/or by curing by chemical reaction.
• Representative equipment and corresponding methods for such use of glass fibers in gun roving are described in U.S. Patent No.
• the chopped pieces are from about 1.27 cm to about 5.08 cm (1/2 to about 2 inches) in length.
• Glass fiber gun roving has heretofore been coated with liquid sizing compositions containing Werner-type chrome complexes, such as methacryl ato chromic chloride, which is thought to function in part at least as a glass-resin coupling agent, although such chrome complexes have sometimes been used together with conventional organosilane glass-resin coupling agents.
• Werner-type chrome complexes such as methacryl ato chromic chloride
• a substantially chrome-free aqueous sizing composition for glass fiber gun roving which comprises (A) a mixture of emulsified film-forming polymers comprising a polymer of vinyl acetate and ethylene, a polymer of vinyl acetate and an epoxy-functional vinyl monomer, and an unsaturated polyester resin; (B) titanium acetyl acetonate;
• the emulsified film forming polymer components of the present invention can be any emulsified polymers of the types called for which will coalesce to form coherent films, and which preferably will so coalesce at normal ambient workplace temperatures.
• a small amount of suitable plasticizar to aid in such coalescence may be blended and co-emulsified with one or more of the polymers, if desired, but it is ordinarily found possible and preferable to select polymers which ⁇ o not require such a ⁇ itives to exhibit advantageous characteristics in use.
• a latently reactive unsaturated plasticizer with the unsaturated polyester resin co ultimately react with this unsaturated polyester and with an unsaturated polyester matrix resin to more intimately bond the glass fibers to each other and to the matrix in which they are imbeo ⁇ ed as reinforcing elements.
• a particularly suitable emulsified polymer of vinyl acetate and ethylene is available as airflex 410 (TM/Air Products end Chemicals Co.), an aqueous emulsion containing about 55% by weight non-volatiles comprising a vinyl acetate-ethylene copolymer having a glass transition temperature of about 2°C. non-ionically emulsified as particles of about 0.3 ⁇ m average diameter.
• a particularly suitable emulsified polymer of vinyl acetate and an epoxy-functional vinyl monomer is available as Resyn 25-1971 (TM/National Starch and Chemical Corp.), an aqueous emulsion containing about 54.5+1% by weight non-volatiles comprising a copolymer of vinyl acetate with about 2% by weight of glycidyl methacrylate non-ionically emulsified.
• a particularly suitable unsaturated polyester resin is available as MR70D (TM/United States Steel Corp.), an approximately 60:40 by weight blend of an unsaturated polyester and diallyl phthalate, a latently reactive plasticizer, which was non-ionically emulsified to form an aqueous emulsion containing about 59% by weight non-volatiles and designated PE-700.
• a particularly suitable titanium acetyl acetonate is available as Tyzor AA (TM/E.I. duPont de Nemours, Inc.) a 75% by weight solution or dispersion of bis(2, 4-pentanedionate-0,0')bis(2-propanolato) titanium in isopropanol .
• a particularly suitable silylated polyamino polyamide hydrochl oride is available as Y-9567 (TM/Union Carbide Corp.) , an 80% by weight dispersion or solution inmetnanol of a hydrochloric acid salt of
• a particularly suitable cationic lubricant is a weak acid salt of a partial fatty amide of a polyamine such as Emery 8750 U (TM/Emery Industries, Inc.) , a 65% by weight aqeuous solution or dispersion of an acetic acid salt of a partial amide of mixed fatty acids having about 6 to 8 carbon atoms with a. polyethylenamine.
• Emery 8750 U TM/Emery Industries, Inc.
• Emery 8750 U TMS 8750 U
• a 65% by weight aqeuous solution or dispersion of an acetic acid salt of a partial amide of mixed fatty acids having about 6 to 8 carbon atoms with a. polyethylenamine The same material nas also been available
• a particularly suitable 3-methacryloxypropyltrimethoxysilane is available in a blend with a proprietary stabilizer as A-174 (TM/Union Carbide Corp.)
• the silane is preferably hydrolyzed in dilute aqueous weak acid before use.
• the titanium acetyl acetonate, the silylated polyaminopolyamide, an ⁇ thecationic lubricant are solubilized by acids and/or lower alcohols, the inclusion of minor additional amounts of alcohols such as methanol, ethanol , propanol , isopropanol , etc. and/or acids such as nydrochioric or acetic may be found desirable.
• the aqueous sizing compositions of tne invention can be prepared following generally accepted mixing practices. These sizing compositions can be applied to the glass fibers using any convenient method.
• the amount of aqueous sizing composition applied is not narrowly critical, but is preferably controlled so as to deposit on the glass fibers a size coating comprising the in situ drieo residue of the aqueous sizing composition of the invention in an ctmount from about 0.5 to about 2 percent of the weight of the glass, taking into account the dilution of the non-volatile components in the aqueous sizing composition and the usual mechanical loss of some of the aqueous composition initially applied to the fibers before it is dried tnereon.
• the aqueous sizing composition is applied to the glass fibers as they are produced by continuous drawing from the melt. While the aqueous sizing composition on the fibers may be at least partially dried before collection into a package, it is entirely satisfactory to gather the wet fibers into strands, preferably witn aoout 100 to about 300 and more preferably about 200 individual fibers to each strand, collecting tn ⁇ se strands into packages as by winding on a collet, whicn also provides tne tension for drawing the fibers, and then neating the package in a conventional circulating hot air oven to drive off volatile materials and deposit the non-volatile components of the sizing composition as a size coating on the fibers whicn will also bind together the individual fibers into a tigntly integrated strand.
• the integrated continuous glass fiber strands can be roved together in weakly integrated roving, preferably of about 30 to about 70 strands each, to produce a continuous glass fiber gun roving. While the diameter of the individual glass fibers is not narrowly critical, diameters from about 10 ⁇ m to about 13 ⁇ m are preferred.
• EXAMP L E 1 P a rt i c ul a r l y adv antag eo us c h rom e- f ree a queo u s s i zi ng c om po s i ti o ns for gl ass f i ber gun rov i ng , representative of the present invention, were prepared according to the following formulations:
• Airflax 410 (55%) 5.10 2.80 5.10 2. 80 Resyn 25-1971 (54.5%) 4.45 2.43 4.45 2 .43 PE-700 (59%) 1.25 0.74 1.25 0.74 Tyzor AA (75%) 1.10 8.82 1.10 0.82
• Both A and B formulations nad non-volatile content of about 6.0+0.5 percent by weight and ph of about 3.5 to 4.9.
• compositions were applied to both H-fibers (about 10.1 to about 11.4 ⁇ m in diameter) and J-fibers (about 11.4 to about 12.7 ⁇ m diameter) with a conventional applicator as they were drawn from the melt, the wet fibers gathered into strands of about 200 individual fibers and wouno into packages on a rotating collet in groups of 4 strands.
• the packages were dried in a conventional circulating hot air oven maintained at about 130°C (265° F) for about 12-14 hours, depending on the size of the package.
• the dried size coating thus deposited on the glass fibers constituted about 1.0 to about 1.3 percent ofthe weight of the glass and tightly integrated the strands.
• the strands from 13 packages of each type of H-fibers and 11 packages of each type of j-fibers ware rove ⁇ separately into weakly integrated gun roving by conventional means.
• the glass fiber gun rovings so produced were found to exhibit exceptionally advantageous combinations of properties, particularly in view of the sizing compositions being chrome-free. Thus, they were found to chop easily and cleanly, to produce advantageously low levels of fuzz and fly, to wet out rapidly and fully with conventional unsaturated polyester matrix resins (the H-fiber roving being especially useful with unfilled matrix resin systems and the J-fiber roving with more viscous filled matrix resin systems, both of wiiich can be chemically thickened, if desired).
• the unsaturateo polyester resin laminates formed with these rovings exhibited excellent tensile strength and modulus, flexura! strength ano modulus both dry and after immersion in boiling water for 24 hours, impact strength, and otner oasirable characteristics.

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• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Surface Treatment Of Glass Fibres Or Filaments (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Glass Compositions (AREA)

Priority Applications (6)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

Country Status (6)

Cited By (4)

Citations (11)

• 1984
  • 1984-09-24 WO PCT/US1984/001525 patent/WO1986001811A1/en active Application Filing
  • 1984-09-24 JP JP50362884A patent/JPS62500242A/ja active Pending
  • 1984-09-24 GB GB08606702A patent/GB2177407B/en not_active Expired
• 1986
  • 1986-03-19 FI FI861152A patent/FI861152A/fi not_active Application Discontinuation
  • 1986-04-15 NO NO861468A patent/NO861468L/no unknown
  • 1986-05-13 SE SE8602166A patent/SE8602166D0/xx not_active Application Discontinuation

Patent Citations (11)

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